Photographic elements comprising thiazolyl couplers capable of forming infrared-absorbing dyes for integral sound track

ABSTRACT

Color photographic motion picture elements adapted to form a multicolor photographic dye image and an integral, infrared-absorbing, dye sound track and comprising 1-hydroxy-2-N-(5-alkyl-thiazol-2-yl)-naphthamide couplers that are capable of forming quinone imine dyes absorbing infrared radiation in the spectral range from about 600 to about 1000 nm by reaction with an oxidized aromatic primary amino developing agent, the thiazol-2- yl group of said naphthamide couplers bearing a 4-para-C 1  -C 4  alkoxyphenyl group or a 4-para-C 1  -C 4  alkylphenyl group, the hydrogen atoms of said C 1  -C 4  alkoxy or C 1  -C 4  alkyl being unsubstituted or at least one of them having been substituted by a halogen atom.

The present invention relates to novel couplers capable of forminginfrared-absorbing dyes, more particularly to couplers capable offorming integral, infrared-absorbing, dye sound tracks in colourphotographic motion picture elements, to photographic colour elementscomprising such couplers, and to materials comprising suchinfrared-absorbing dyes.

The photographic image as well as the sound track image inblack-and-white motion picture projection films are known to consist ofsilver usually, the sound information in the sound track being presentin the form of periodical variations in density or of periodicalvariations in the ratio between areas that are completely dark and areasthat are fully bright. This sound information can be read optically by aphotocell detecting infrared radiation that has been modulated bypassing through these variations in density or in area. The photocellscustomarily used for this purpose are i.a. the S-1 photocells, whichhave a maximum sensitivity in the infrared region of the spectrum, moreparticularly in the infrared region from about 750 to about 850 nm, inwhich region silver absorbs uniformly.

Although in sound tracks of colour motion picture projection filmssilver has been used customarily, the application of silver thereinrequires special selective treatments including a separate developmentof the sound track portion. To avoid such special selective treatmentsattempts have been made to use dyes instead of silver for the soundtracks of colour motion picture projection films. This allows theformation of both a dye image and a dye sound track during the same andonly colour development step. The dye that builds up the sound track isa quinone imine coupling product that should have peak absorption in theinfrared region where the photocells, e.g. the S-1 photocells, aresensitive, namely from about 750 to about 850 nm.

Infrared-absorbing dyes that can be used at least partially in integraldye sound tracks have been disclosed in U.S. Pat. No. 2,266,452, U.S.Pat. No. 2,373,821, JP PU 59,838, UK P 1,424,454, U.S. Pat. No.3,458,315, U.S. Pat. No. 3,476,563, UK P 519,208, in Research DisclosureN°13460 of June 1975, N°15125 of November 1976, and N°18732 of November1979.

U.S. Pat. No. 4,178,183 teaches the use of1-hydroxy-2-N-(4-phenyl-5-ballasted-thiazol-2-yl)-naphthamide couplersfor forming integral, infrared-absorbing, dye sound tracks in colourphotographic motion picture elements.

However, the absorption peaks of the infrared-absorbing dyes hithertoused for integral dye sound tracks are not broad enough and areinsufficiently bathochromic. Their peak absorption usually lies between800 and 820 nm. In these circumstances silver is still needed at leastpartially to guarantee sufficient absorption in the sensitivity range ofthe S-1 photocells and to ensure sufficient density. Moreover, the useof these dyes gives rise to a loss in output of the sound track.

It is therefore an object of the present invention to provide 2- or4-equivalent couplers that are capable of forming dyes that haveenhanced infrared peak absorption, have a broadened more bathochromicabsorption range that encompasses the sensitivity range of the S-1photocells, and are not subject to loss in output of the sound track.

It is another object of the present invention to provide colourphotographic motion picture elements comprising such couplers that arecapable of forming infrared-absorbing dyes for integral dye sound trackswithout requiring special selective treatment as above referred to, andwhich have sufficient density in the absence of silver and show nosignificant loss in output of the sound track.

It is a further object of the present invention to provide dyes thathave a high infrared peak absorption and offer a broadened morebathochromic absorption range than the known infrared-absorbing dyes.

Other objects of the present invention will become apparent from thedisclosure herein.

The above objects are accomplished by the use, in colour photographicmotion picture elements, adapted to form a multicolour photographic dyeimage and an integral, infrared-absorbing, dye sound track, of at leastone 1-hydroxy-2-N-(5-alkyl-thiazol-2-yl)-naphthamide coupler that iscapable of forming an infrared-absorbing quinone imine dye by reactionwith an oxidized aromatic primary amino developing agent, thethiazol-2-yl group of said naphthamide couplers bearing a 4-paraphenylgroup or a 4-para-C₁ -C₄ alkylphenyl group, the hydrogen atoms of saidC₁ -C₄ alkoxy or C₁ -C₄ alkyl being unsubstituted or at least one ofthem having been substituted by a halogen atom.

1-Hydroxy-2-N-(5-alkyl-thiazol-2-yl)-naphthamide couplers, which can beprepared very simply and are very interesting from an economicalstandpoint, are those corresponding to the following general formula:##STR1## wherein represent:

R--a C₁ -C₄ alkoxy group e.g. methoxy and ethoxy, a C₁ -C₄ alkyl groupe.g. methyl, or a C₁ -C₄ alkoxy group or C₁ -C₄ alkyl group wherein atleast one of the hydrogen atoms has been replaced by a halogen atom suchas fluorine e.g. difluoromethoxy;

Y--an alkyl group having at least 8 carbon atoms e.g. tetradecyl, whichrenders the coupler fast to diffusion in hydrophilic colloid media;

Z--hydrogen or a substituent, e.g. a chlorine atom, that splits offduring the coupling reaction, thus conferring 2-equivalent character tothe coupler.

In addition to chlorine, other interesting substituents that may confer2-equivalent character to the naphthamide couplers of the presentinvention are e.g. an acyloxy group, an alkoxy group, an aryloxy group,a heterocycloxy group, an alkylthio group, an arylthio group e.g.phenylthio and carboxyphenylthio, an alkylsulphonyl group, anarylsulphonyl group, an alkylsulphinyl group, an arylsulphinyl group, analkyl- or aryl-substituted carbonylmethoxy group, an alkoxy- oraryloxy-substituted carbonylmethoxy group, and a heterocyclic thio groupsuch as a tetrazolylthio group.

The present invention provides a photographic element comprising asupport and a plurality of photosensitive silver halide emulsion layersfor forming a multicolour photographic dye image and an integral,infrared-absorbing, dye sound track, one of said photosensitive silverhalide emulsion layers or a non-photosensitive hydrophilic colloid layerin water-permeable relationship therewith, comprising at least onedispersed 1-hydroxy-2-N-(5-alkylthiazol-2-yl)- naphthamide couplercapable of forming an infrared-absorbing quinone imine dye by reactionwith an oxidized aromatic primary amino developing agent characterizedin that said naphthamide coupler bears on the thiazol-2-yl group a4-paraC₁ -C₄ alkoxyphenyl group or a 4-para-C₁ -C₄ alkylphenyl group,the hydrogen atoms of said C₁ -C₄ alkoxy or C₁ -C₄ alkyl beingunsubstituted or at least one of them having been substituted by ahalogen atom.

According to one embodiment of the present invention a photographicelement is provided, which comprises:

a support,

an image-recording layer pack comprising in any desired sequence atleast one image-recording blue-sensitive gelatin silver halide emulsionlayer containing at least one yellow image dye-forming coupler, at leastone image-recording red-sensitized gelatin silver halide emulsion layercontaining at least one cyan image dye-forming coupler, at least oneimage-recording green-sensitized gelatin silver halide emulsion layercontaining at least one magenta image dye-forming coupler, and one ormore intermediate layers between said image-recording emulsion layers,

a photosensitive sound-recording gelatin silver halide emulsion layer,and

an antistress layer,

said photosensitive sound-recording layer and/or a non-photosensitivehydrophilic colloid layer in water-permeable relationship therewithcomprising said 1-hydroxy-2-N-(5-alkyl-thiazol-2-yl)-naphthamidecoupler.

The present invention further also provides infrared-absorbing quinoneimine dyes formed by a coupling reaction between an oxidized aromaticprimary amino compound and the said 1-hydroxy-2-N-(5-alkylthiazol-2-yl)-naphthamide coupler.

Representative examples of1-hydroxy-2-N-(5-alkyl-thiazol-2-yl)-naphthamide couplers that can beused in accordance with the present invention are listed in thefollowing Table 1, the symbols used therein referring to the abovegeneral formula.

                  TABLE 1                                                         ______________________________________                                                                              Melting                                 Coupler No.                                                                            R            Y         Z     point                                   ______________________________________                                        1        methoxy      tetradecyl                                                                              chloro                                                                              138                                     2        ethoxy       tetradecyl                                                                              chloro                                                                              150                                     3        difluoromethoxy                                                                            tetradecyl                                                                              chloro                                                                              143                                     4        methyl       tetradecyl                                                                              chloro                                                                              136                                     ______________________________________                                    

The novel couplers according to the present invention can be prepared bytechniques well known to those skilled in the art e.g. according to thefollowing general reaction scheme by first performing a cyclizationreaction of appropriately substituted α-bromo-alkanoylbenzenederivatives with thiourea to form the corresponding 2-aminothiazoles andnext to carry out a condensation of phenyl-1-hydroxynaphthoates, whichmay carry a coupling off substituent in the 4-position, with these2-aminothiazoles. In the following general reaction scheme, R has thesignificance as defined under the above general formula. ##STR2##

According this reaction scheme the1-hydroxy-2-N-(5-alkyl-thiazol-2-yl)-naphthamide couplers correspondingto the above general formula can be prepared very simply and veryeconomically.

It was surprising to find that among the many substituents on thethiazol-2-yl group, which have been studied, only the above-specifiedalkoxyphenyl and alkylphenyl substituents of the couplers of the presentinvention made it possible to form quinone imine dyes having infraredabsorption characteristics significantly better than those of the knowncouplers not containing the said specific substituents. The infraredabsorption range of the quinone imine dyes formed in accordance with thepresent invention extends from the red region at about 600 nm to wellinto the infrared region at about 1000 nm. This absorption rangeconsequently covers the entire sensitivity range of the S-1 photocells.Moreover, the broadening of the absorption peak with increasing colourdensity is considerable and progressive. The density values obtainedwith the quinone imine dyes formed in accordance with the presentinvention are much more favourable than those obtained with the knownquinone imine dyes. In general, the maximum dye density of these quinoneimine dyes produced throughout the spectral region of from 750 to 850 nmmay exceed 1.5. The signal-to-noise ratio of the dye sound tracks madein accordance with the present invention is better than that of knowndye sound tracks. Heat stability tests and dark-fading tests have provedthat the heat and light stability of the infrared-absorbing sound trackdyes obtained from the couplers used in accordance with the presentinvention are very good and that the loss in density of the dye tracksduring ageing is very low.

The couplers according to the present invention can thus be usedadvantageously in a hydrophilic colloid layer of colour photographicmotion picture elements for forming infrared-absorbing dyes for integraldye sound tracks. The couplers of the present invention can beincorporated successfully into a hydrophilic colloid layer by dissolvingthem first in at least one water-immiscible, oil-type solvent oroil-former, adding the resulting solution to an aqueous phase containinggelatin and a dispersing agent, passing the mixture through ahomogenizing apparatus so that a dispersion of the oily coupler solutionin an aqueous medium is formed, mixing the dispersion with a hydrophiliccolloid composition e.g. a gelatin silver halide emulsion, and coatingthe resulting composition in the usual manner to produce a system inwhich particles of coupler, surrounded by an oily membrane, aredistributed throughout the gel matrix. The dissolution of the coupler inthe oil-former may be facilitated by the use of an auxiliary low-boilingwater-immiscible solvent, which is removed afterwards by evaporation.

The couplers according to the present invention can be dispersed inhydrophilic colloid compositions with the aid of at least one knownoil-formers such as an alkyl ester of phthalic acid, e.g. dimethylphthalate, diethyl phthalate, di-n-butyl phthalate, di-i-amyl phthalate,dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, dinonylphthalate, didecyl phthalate, n-amyl phthalate,dibutylmonochlorophthalate, butylphthalylbutyl glycolate,2,4-di-n-amylphenol, 2,4-di-tert-amylphenol, a phosphoric acid acidester e.g. diphenyl phosphate, triphenyl phosphate, tri-o, m-, orp-cresyl phosphate, o-cresyl diphenyl phosphate, dioctyl phosphate,di-octyl butyl phosphate, tri-n-octyl phosphate, tri-ndecyl phosphate,trixylenyl phosphate, tris-(isopropylphenyl)phosphate, tributylphosphate, trihexyl phosphate, trinonyl phosphate, trioleyl phosphate,tris-(butoxyethyl)phosphate, a citric acid ester e.g.O-acetyltriethyl-(or butyl-, hexyl-, octyl-, nonyl-, or decyl)-citrate,a benzoic acid ester e.g. butyl (or hexyl-, heptyl-, octyl-, nonyl-,decyl-, undecyl-, dodecyl-, tridecyl-, tetradecyl-, hexadecyl-,octadecyl-, oleyl-, etc.) benzoate, n-butyl-2-methoxy benzoate,pentyl-o-methyl benzoate, decyl-pmethyl-benzoate,octyl-o-chlorobenzoate, lauryl-p-chlorobenzoate,propyl-2,4-dichlorobenzoate, octyl-2,4-dichlorobenzoate,stearyl-2,4-dichlorobenzoate, oleyl-2,4-dichlorobenzoate,octyl-p-methoxybenzoate, a fatty acid ester e.g. hexadecyl myristate,dibutoxyethyl succinate, dioctyl adipate, dioctyl azelate,decamethylene-1,10-diol diacetate, triacetin, tributyrin, benzylcaprate, pentaerythrite tetracapronate, isosorbide dicaprylate, an amidee.g. N,N-dimethyl lauramide, N,N-diethyl lauramide, N,N,di-n-butyllauramide, N-butylbenzene sulphonamide, trioctyl trimellitate, achlorinated paraffin, an aliphatic ester of glycerol and derivativesthereof e.g. glycerol triacetate, ethers e.g. allyl ether, or anoil-former as described in i.a. U.S. Pat. Nos. 2,304,940; 2,322,027;2,353,262; 2,533,514; 2,801,170; 2,801,171; 2,835,579; 2,852,383;2,949,360; 3,287,134; 3,554,755; 3,700,454; 3,748,141; 3,767,142;3,779,765; 3,788,857; 3,837,863; 3,936,303; 4,004,928; 4,075,022;4,106,940; 4,178,183; 4,233,389; 4,250,251; in UK P 958,441; 1,222,753;1,272,561; 1,424,454; 1,501,233; 2,027,130; in DE OS 2,432,041;2,538,889; 2,613,504; 2,629,842; 2,903,681; 2,909,402; 2,932,368; in DEP 1,152,610; in JA P 23233/71; 29461/74; 28693/77; 15127/78; 1521/78, inJA Pat.Publications 34715/77; 82078/75; 26037/76; 27921/76; in BE P768,585 and 833,202, and in the Research Disclosures 18732 (Nov. 1979)p. 634-38 and 16745 (March 1978) p. 58-59.

The couplers according to the present invention can be dispersed easilyin hydrophilic colloid compositions with the aid of at least onehigh-boiling substantially water-insoluble oilformer of the class ofsubstituted 2-propanols and carboxylic; phosphoric, and phosphonic acidesters thereof as disclosed in U.S. Pat. No. 4,430,422. Among theseoil-formers, which can be used in combination with the couplersaccording to the present invention, the carboxylic acid acid esters andespecially the 2-ethylhexanoic acid ester of1,3-di-n-octyloxy-2-propanol, the myristic acid ester of 1,3-di-methoxy-2-propanol, the 2-ethylhexanoic acid ester of 1-n-butoxy-3-(2'-ethyl)-n-hexyloxy-2-propanol, the myristic acid ester of1-methoxy-2-pro- panol, and the 2-ethylhexanoic acid ester of1,3-di-n-hexyloxy-2-propanol offer the best results. The combination ofthe couplers according to the present invention with these especiallyidentified oil-formers results in additional advantages in that an evenhigher bathochromic shift as well as a strong oppression of opalescencemay be obtained.

The couplers according to the present invention can also be dispersed inhydrophilic colloid compositions with the aid of a combination of atleast one of the above-mentioned known oil-formers and at least one ofthe above-mentioned high-boiling substantially water-insolubleoil-formers of the class of substituted 2-propanols and carboxylic,phosphoric, and phosphonic acid esters thereof.

For dispersing the couplers according to the present invention, theoil-formers, especially those of the class of substituted 2-propanolsand carboxylic, phosphoric, and phosphonic acid esters thereof can beused in widely varying concentrations e.g. in amounts ranging from about0.1 to about 10 parts by weight and preferably from 0.5 to 2 parts byweight relative to the amount of the couplers dispersed therewith.Excellent results were obtained with 0.5 part by weight of theoil-formers relative to 1 part of the couplers of the invention. Forinstance, very good results were obtained with a fine-grain silverhalide sound-recording emulsion comprising per sq. m. an amount ofsilver that is equivalent with 0.6 g of silver nitrate, 0.8 g of coupleraccording to the invention, and 0.4 g of preferentially used oil-former.

Inasmuch as the nature and the concentration of the oil-formers may havean influence on the absorption characteristics of the quinone imine dyesobtained from the couplers according to the invention, it may thus bepossible to adjust the absorption spectrum of these dyes in a desiredsense by establishing the optimum oil-former composition and adjustingthe concentration of said preferentially used oil-formers.

It may be useful to combine at least one of the above definedoil-formers with at least one auxiliary solvent that is insoluble oralmost insoluble in water and has a boiling point of at most 150° C.,such as lower alkyl acetates e.g. methyl acetate, ethyl acetate,n-propyl acetate, isopropyl acetate, butyl acetate, ethyl formiate,methyl propionate, ethyl propionate, carbon tetrachloride,sym-dichloroethylene, trichloroethylene, 1,2-dichloropropane,chloroform, amyl chloride, diethyl carbonate, diethyl ketone; methylethyl ketone, methyl-n-propylketone, diethyl ketone, diisopropyl ether,cyclohexane, methylcyclohexane, ligroin, benzene, toluene, xylene,nitromethane. The auxiliary solvent may also be a water-soluble organicsolvent such as methanol, ethanol, isopropanol, dimethylsulphoxide,tetrahydrofuran, N-methylpyrrolidone, dioxan, acetone, butyrolactone,ethylene glycol, ethylene glycol monomethyl ether, ethylene glycolmonoethyl ether, ethylene glycol monobutyl ether, diethylene glycolmonoethyl ether, diethylene glycol monomethyl ether, glycerol,acetonitrile, formamide, dimethylformamide, tetrahydrothiophene dioxide,or dimethoxyethane. The auxiliary solvent may also be one described ini.a. U.S. Pat. Nos. 2,801,170; 2,801,171; 2,949,360; 2,835,579.

For processing the colour photographic motion picture elements forforming the image dyes as well as the infrared-absorbing dyes forintegral dye sound tracks any conventional colour developing agent canbe employed. Inasmuch as the colour developing agent will react inoxidized form with i.a. the couplers used in accordance with the presentinvention, the nature of the particular colour developing agent will, ofcourse, also determine the characteristics of the infrared-absorbingdyes obtained therewith. Colour developing agents that are very wellsuited for processing the colour photographic motion picture elementscomprising the couplers of the present invention are e.g.2-amino-5-diethylamino-toluene hydrochloride (CD-2),2-amino-5-[N-ethyl-N-(methylsulphonylamino)-ethyl]aminotoluene sulphate(CD-3), 4-amino-3-methyl-N-ethyl-N( -hydroxyethyl)aniline sulphate(CD-4), and N,N-diethyl-p-phenylene diamine sulphate (TSS).

The colour photographic motion picture elements comprising the couplersof the present invention can be of the positive print film type or ofthe reversal film type.

Further details on the formation of integral infrared-absorbing soundtracks in photographic elements and on the infrared-absorbing quinoneimine dyes obtained therewith as coupling product in a separate layer ofsuch photographic elements during the same processing step as the onewherein the colour image is formed, can be found in U.S. Pat. Nos.4,178,183; 4,233,389; 4,250,251 ; 4,430,422 and in the ResearchDisclosures 18 732 (Nov. 1979) p. 634-638; 15 125 (Nov. 1976) p. 24-25;13 460 (June 1975) p. 50.

Such sound-recording layer(s) should have a spectral or generalsensitivity such that an undesired image is not formed on image-wiseexposure of the image-recording layers.

The couplers of the present invention used for forminginfrared-absorbing quinone imine dyes can be incorporated into a layerof the sound-recording layer unit making part of a colour photographicmotion picture element. Such element may consist e.g. of asound-recording layer unit comprising at least one sound-recordingphotosensitive gelatin silver halide emulsion layer coated on top of theimage-recording layers.

A common layer composition of a colour photographic motion pictureelement comprises in order of sequence : a film support, theblue-sensitive silver halide emulsion layer(s) containing yellow-formingcolour coupler(s), optionally (an) intermediate layer(s), thered-sensitized silver halide emulsion layer(s) containing cyan-formingcolour coupler(s), optionally (an) intermediate layer(s), and thegreen-sensitized silver halide emulsion layer(s) containingmagenta-forming colour coupler(s). The sound-recording layer(s) can havedifferent locations as specified hereinafter, e.g. they can be coated ontop of the green-sensitized layer(s).

Different sound-recording silver halide compositions are possible. Forinstance, the sound-recording silver halide emulsion is sensitive toultraviolet radiation alone, or to infrared radiation, or to radiationof the spectral region between 470 and 500 nm. What is important is thatduring the image exposure of the colour element the sound-recordinglayer does not respond. In these cases the sound-recording layer can becoated directly on the uppermost green-sensitized layer.

According to another alternative the sound-recording layer can besensitive to the blue spectral region, but to a far less extent than theblue-sensitive layer(s) containing the yellow-forming couplers so thatduring the image exposure of the colour photographic motion pictureelement the sound-recording layer does not respond. The blue-sensitivesound-recording layer, which can e.g. be a fine-grain silverchlorobromide emulsion sensitive in the spectral range from 400 to 470nm, may comprise a cyan-forming coupler in addition to the couplerforming an infrared-absorbing dye. When an additional cyan-formingcoupler is used, the reaction with oxidized developer leads to theformation of a cyan dye in addition to the infrared-absorbing dyeaccording to the invention. Cyan dyes are known to absorb also in thelower infrared region. The combined infrared absorption of both dyesthus increases the infrared absorption range and the density.

Likewise according to a further alternative the sound-recording layercan be sensitive to the green spectral region, but to a far less extentthan the green-sensitized layer so that during the image exposure of thecolour photographic motion picture element the sound-recording layerdoes not respond.

According to a further alternative the sound-recording layer can besensitive to the red spectral region.

The sound-recording layer can be sensitive to both the red and greenspectral regions, but to a far less extent than the image-recordingred-sensitized and green-sensitized layer(s) so that during the imageexposure of the colour photographic motion picture element thesound-recording layer does not respond.

According to all these above-mentioned embodiments the sound-recordinglayer contains one or more couplers for forming infrared-absorbing dyesound tracks.

According to a further embodiment the colour photographic motion pictureelement comprises in order of sequence a film support, theblue-sensitive silver halide emulsion layer(s) containing yellow-formingcolour coupler(s), optionally (an) intermediate layer(s), thered-sensitized silver halide emulsion layer(s) containing cyan-formingcolour coupler(s), optionally (an) intermediate layer(s), thesound-recording silver halide emulsion layer(s) containing coupler(s)forming infrared-absorbing dye(s) in accordance with the invention,optionally (an) intermediate layer(s), the green-sensitized silverhalide emulsion layer(s) containing magenta-forming colour couplers, andif desired (an) antistress layer(s). According to this embodiment thesound-recording silver halide emulsion layer(s) containing coupler(s)forming infrared-absorbing dye(s) in accordance with the invention is(are) sensitive in the blue spectral region from 400 to 470 nm, but is(are) far less sensitive than the blue-sensitive silver halide emulsionlayer(s), and it (they) may contain in addition to the coupler(s)forming infrared-absorbing dye(s) (a) cyan-forming colour coupler(s) asalready described above. The silver halide of this (these)sound-recording emulsion layer(s) may be silver chloride orchlorobromide, preferably fine-grain silver chloride comprising 0-40 mol% bromide and 0-5 mol % iodide.

According to a different embodiment the colour photographic motionpicture element does not encompass a separate sound-recording layercontaining a coupler that is capable of forming infrared-absorbing dyes.Instead thereof the latter couplers can be incorporated e.g. togetherwith magenta-forming coupler(s) into the green-sensitized layer(s).However, the coupling speed of the magenta-forming couplers should thensubstantially exceed the coupling speed of the couplers forming thesound track dyes, so that in case of a normal image-wise exposure, thelatter couplers, which are slow-coupling, cannot be affected as a resultof insufficient amounts of oxidized developer. During the intensivesound track exposure both kinds of couplers respond and form theirrespective dyes, but the S-1 photocells only react to the infrareddensity obtained. Alternatively, the couplers that are capable offorming infrared-absorbing dyes can be incorporated together with thecyan image-forming coupler(s) into the red-sensitized layer(s). Duringthe intensive sound track exposure both kinds of couplers respond andform their respective dyes, but the S-1 photocells again only react tothe infrared density obtained.

In all above-mentioned embodiments the uppermost emulsion layer may, ofcourse, be protected by (an) antistress layer(s).

Further details on layer structures of colour photographic motionpicture elements can be found in U.S. Pat. Nos. 3,705,799 - 3,705,801 -3,737,312, and 4,208,210; in DE-OS 2,302,661; in UK-P 1,411,311 -1,429,108, and in the Research Disclosure 18 732 (November 79) p.634-38.

Although in the making of dispersions of the couplers of the inventionin hydrophilic colloid compositions gelatin is favoured as hydrophiliccolloid, other water-soluble colloidal substances or mixtures of thesecan be used too e.g. colloidal albumin, starch, zein, alginic acid andderivatives thereof, such as salts, esters, and amides, casein,cellulose derivatives such as carboxymethyl cellulose, synthetichydrophilic colloids such as polyvinyl alcohol, poly-N-vinylpyrrolidone, anionic polyurethans, copolymers of acrylic esters,acrylonitrile, and acrylamides, etc.

During the manufacture of the colour photographic silver halide motionpicture element according to the invention, the couplers correspondingto the above general formula can be incorporated in the presence of atleast one of the above defined oil-formers into the coating compositionof the silver halide emulsion layer(s) or other colloid layer(s) inwater-permeable relationship therewith according to any technique knownby those skilled in the art of incorporating couplers, into colloidcompositions. For more details about particularly suitable techniquesthat can be employed for dispersing the couplers of the invention intohydrophilic colloid compositions there can be referred to U.S. Pat. Nos.2,304,939; 2,304,940; 2,322,027; 2,801,170; 2,801,171; and 2,949,360.

The couplers of the invention can be dispersed in the presence of asurface-active agent or dispersing aid. The surface-active agent usedmay be of the ionic, non-ionic or amphoteric type. Examples of suitableionic surface-active agents are the sodium salt of oleylmethyltauride,sodium stearate, 2-heptadecyl-benzimidazole-5-sulphonic acid sodiumsalt, sodium sulphates of aliphatic alcohols containing more than 5carbon atoms per molecule, e.g. 2-methylhexanol sodium sulphate; thesodium salt of di-isooctyl ester of sulphonated succinic acid, sodiumdodecyl sulphate and p-dodecylbenzene sulphonic acid sodium salt.Examples of suitable non-ionic surface-active agents are saponine,condensation products of ethylene oxide and alkyl phenols, e.g.p-octylphenol and p-isononyl phenol and phenylethylene glycol oleate.Other examples of anionic and non-ionic surface-active agents can befound in UK P 1,460,894.

A survey of surface-active agents, representatives of which can be usedin dispersing the couplers of the present invention, was made by GerhardGawalek in "Wash- und Netzmittel" Akademieverlag, Berlin (1962).

It is also possible to use mixtures of anionic and non-ionicsurface-active agents as described e.g. in UK P 1,460,894.

Other interesting surface-active agents that can be used in dispersingthe couplers of the invention are the short-chain fluorine-containingsurface-active agents disclosed in U.S. Pat. No. 4,292,402.

The photosensitive silver halide emulsions used in the making of colourphotographic motion picture elements according to the present inventioncan be sensitized chemically as well as optically. They can besensitized chemically by carrying out the ripening in the presence ofsmall amounts of sulphur-containing compounds such as allyl thiocyanate,allyl thiourea, or sodium thiosulphate. The emulsions can also besensitized by means of reducing agents e.g. tin compounds as describedin FR P 1,146,955 and in BE P 568,687, imino-aminomethane sulphinic acidcompounds as described in UK P 789,823 and small amounts of noble metalcompounds such as gold, platinum, palladium, iridium, ruthenium, andrhodium compounds. They can be sensitized optically by means of cyanineand merocyanine dyes.

The emulsions can also comprise compounds that sensitize the emulsionsby development acceleration e.g. compounds of the polyoxyalkylene typesuch as alkylene oxide condensation products as described i.a. in U.S.Pat. No. 2,531,832 - 2,533,990, in UK P 920,637; 940,051; 945,340;991,608 and 1,091,705, onium derivatives of amino-N-oxides as describedin UK P 1,121,696, and thioethers as described in U.S. Pat. No.4,292,400. Further, the emulsions may comprise stabilizers e.g.heterocyclic nitrogen-containing thioxo compounds such asbenzothiazoline-2-thione and 1-phenyl-2-tetrazoline-5-thione andcompounds of the hydroxytriazolopyrimidine type. They can also bestabilized with an aromatic or heterocyclic mercapto compound asdescribed in the UK PA 39457/80 or with mercury compounds such as themercury compounds described in BE P 524,121; 677,337, and in the UK P1,173,609.

The hydrophilic colloid layers, in particular the photosensitiveemulsions layers, making part of the colour photographic motion pictureelements of the present invention may be hardened, if desired, with theaid of known hardening agents. Particularly interesting hardeningresults were obtained with hardening agents corresponding to thefollowing general formula: ##STR3## wherein:

each of R¹ and R² (same or different) represent hydrogen, a C¹ -C³ alkylgroup, an aryl group e.g. phenyl, an aryl group substituted with a loweralkyl group or with halogen e.g. phenyl substituted with methyl, ethyl,chloro, or bromo, an aralkyl group e.g. benzyl, an aralkyl groupsubstituted with a lower alkyl group or with halogen, or

R¹ and R² together represent the atoms necessary to complete a saturatedheterocyclic group, preferably morpholino or piperidino, said saturatedheterocyclic group optionally being substituted with a lower alkyl groupor with halogen e.g. methyl, ethyl, chloro, or bromo,

R³ hydrogen, methyl, or ethyl, and

X a chemical bond or a C₁ -C₃ group e.g. methylene, ethylene, orpropylene.

The photosensitive emulsions containing the couplers of the inventionmay also comprise any other kind of ingredient such as those describedfor such emulsions in Research Disclosure no. 17,643 of December 1978.

The emulsions can be coated on a wide variety of photographic emulsionsupports. Typical supports include cellulose ester film, polyvinylacetalfilm, polystyrene film, polyethylene terephthalate film and relatedfilms or resinous materials.

The infrared-absorbing dye sound tracks produced in the colourphotographic motion picture elements of the present invention are equalin fidelity with known silver sound tracks. No higher gain is requiredto achieve comparable decibel output, since the dye sound tracksproduced in accordance with the invention--unlike known dye soundtracks--have a maximum density that is of substantially the same valueas that of silver sound tracks.

The infrared-absorbing quinone imine dyes formed by a coupling reactionof 1-hydroxy-2-N-(5-alkyl-thiazol-2-yl)-naphthamide couplers accordingto the present invention with an oxidized aromatic primary aminocompound can be used also as filter dyes in non-photographic materialssuch as in glass or synthetic resin materials e.g. in window glass ascommonly used in shop and office windows for filtering the sun rays. Itis obvious that the infrared-absorbing dyes obtained in accordance withthe invention may find other interesting applications.

The following examples illustrate the present invention.

EXAMPLE 1

Samples of colour photographic motion picture elements were made, allthe samples being identical except for the composition of theirsound-recording layer. The difference in the composition of thesound-recording layers only referred to the nature of the coupler andthe oil-former used therein. The samples had the following layersequence:

black antihalation layer

transparent film support

subbing layer

image-recording blue-sensitive gelatin silver halide emulsion layercontaining a yellow image dye-forming coupler

gelatin intermediate layer

image-recording red-sensitized gelatin silver halide emulsion layercontaining a cyan image dye-forming coupler

sound-recording chlorobromide emulsion layer sensitive in the bluespectral region from 400 to 470 nm and comprising silver in an amountequivalent to 0.6 g of silver nitrate per sq. m., 1.5 g/sq. m. ofgelatin and 0.75 g/sq. m. of coupler, as defined in Table 2, dispersedwith the aid of an equal weight of oil-former, also defined in Table 2hereinafter

image-recording green-sensitized gelatin silver halide emulsion layercontaining a magenta image dye-forming coupler

antistress layer.

The couplers and oil-formers used in the sound-recording layer of thesamples are identified in the following Table 2. The comparison A is1-hydroxy-2-N-(4-phenyl-5-thiazol-2-yl)-naphthamide, which is the4-equivalent coupler described in Example 1 of U.S. Pat. No. 4,178,183,and comparison B has the same structure as comparison A except that itis 2-equivalent and as a consequence carries a coupling off group, whichin the present case is a chloro substituent at the 4-position of thenaphthamide ring system. Couplers 1, 2, and 4 are couplers according tothe present invention, identified in Table 1. In the same tablereference is made also to the accompanying FIGS. 1 to 8, which show adensity versus wavelength (in nm) plot obtained from the measurement onthe sound track quinone imine dye formed as described hereinafter.

                  TABLE 2                                                         ______________________________________                                                                       refer to                                       Coupler   Oil-former           FIG. No.                                       ______________________________________                                        Comparison A                                                                            dibutyl phthalate    1                                              Comparison B                                                                            dibutyl phthalate    2                                              Coupler 1 dibutyl phthalate    3                                              Coupler 1 1,3-dimethoxy-2-propanol                                                                           4                                                        myristic ester                                                      Coupler 1 1,3-di-n-octyloxy-2-propanol                                                                       5                                                        2-ethylhexanoic ester                                               Coupler 1 1-n-butoxy-3-(2'-ethyl)-n-hexyloxy-                                                                6                                                        2-propanol 2-ethylhexanoic ester                                    Coupler 2 1,3-di-n-octyloxy-2-propanol                                                                       7                                                        2-ethylhexanoic ester                                               Coupler 4 1,3-di-n-octyloxy-2-propanol                                                                       8                                                        2-ethylhexanoic ester                                               ______________________________________                                    

All samples were exposed similarly to white light having a colourtemperature of 3200° K., to be recorded in the image-recording layersand then exposed again in the sound track area to light so as to affectthe sound-recording layer.

The exposed samples were then processed as described hereinafter, nospecial selective treatment being given to the sound-recording layer.The processing was as follows:

The samples were rinsed for 15 s in a prebath at 27° C. having thefollowing composition:

    ______________________________________                                        water               800      ml                                               borax               20       g                                                anhydrous sodium sulphate                                                                         100      g                                                sodium hydroxide    1        g                                                water to make       1000     ml                                                                 (pH 9.25 at 27° C.)                                  ______________________________________                                    

The black antihalation layer was removed with water at 27° C. Next, thesamples were immersed for 3 min in a colour developing bath at 36.7° C.(±0.1) having the following composition:

    ______________________________________                                        water                800       ml                                             calcium-sequestering agent                                                                         1         ml                                             anhydrous sodium sulphite                                                                          4.35      g                                              2-amino-5-diethylamino-toluene                                                                     2.95      ml                                             hydrochloride                                                                 anhydrous sodium carbonate                                                                         17.10     g                                              anhydrous sodium bromide                                                                           1.72      g                                              7 N sulphuric acid   0.62      ml                                             water to make        1000      ml                                                                (pH 10.53 at 27° C.)                                ______________________________________                                    

The samples were then treated with the following stopbath for 40 s at27° C.:

    ______________________________________                                        water              900      ml                                                7 N sulphuric acid 50       ml                                                water to make      1000     ml                                                                 (pH 0.9 at 27° C.)                                    ______________________________________                                    

The samples were then bleached in the following bath for 1 min at 27°C.:

    ______________________________________                                        water                   900      ml                                           anhydrous potassium hexacyanoferrate (III)                                                            30       g                                            anhydrous sodium bromide                                                                              17       g                                            water to make           1000     ml                                                                 (pH 6.5 at 27° C.)                               ______________________________________                                    

The bleached samples were rinsed in water for 40 s at 27° C. and nestimmersed in the following fixing bath for 40 s at 27° C.:

    ______________________________________                                        water                  800      ml                                            58% aqueous solution of ammonium                                                                     100      ml                                            thiosulphate                                                                  anhydrous sodium sulphite                                                                            2.50     g                                             anhydrous sodium hydrogen sulphite                                                                   10.30    g                                             water to make          1000     ml                                                                 (pH 5.8 at 27° C.)                                ______________________________________                                    

Finally, the samples were rinsed for 1 min in water at 27° C., immersedfor 10 s in the following stabilizing bath at 27° C., and allowed todry:

    ______________________________________                                        water                    900    ml                                            37.5% aqueous solution of formaldehyde                                                                 15     ml                                            stabilizer additive      0.14   ml                                            water to make            1000   ml.                                           ______________________________________                                    

In consequence of the high density values obtained in the sound tracks,the signal to noise ratio of the dye sound tracks made in accordancewith the present invention exceeds that of known dye sound tracks.

Comparable results were obtained with the other couplers of the presentinvention, which are identified in Table 1 hereinbefore given.

As a consequence of these higher standards reached with the couplers ofthe present invention, it is possible to use an image- andsound-recording colour photographic motion picture element in which thesound record is processed simultaneously with the image record using thesame baths, the sound record entirely consisting of aninfrared-absorbing quinone imine dye as described above.

Dark-fading tests of the quinone imine dyes obtained in accordance withthe present invention proved that their heat and light stability wasexcellent and that the loss in density during ageing was very low.

Alternatively, the samples, instead of being bleached with the abovehexacyanoferrate (III) bleach bath, could be bleached also withpersulphate-based baths by first treating them with the followingaccelerator bath:

    ______________________________________                                        water                 900      ml                                             anhydrous sodium metabisulphite                                                                     3.3      g                                              glacial acetic acid   5.0      ml                                             persulphate bleach accelerator                                                                      3.3      g                                              ethylene diamine tetraacetic acid                                                                   0.5      g                                              tetrasodium salt                                                              water to make         1000     ml                                                                 (pH 4.0 at 27° C.)                                 ______________________________________                                    

and next with the following bleach bath:

    ______________________________________                                        water                  850      ml                                            chlorine scavenger     0.35     g                                             sodium persulphate     33       g                                             sodium chloride        15       g                                             anhydrous sodium dihydrogen phosphate                                                                7.0      g                                             85% phosphoric acid    2.5      ml                                            water to make          1000     ml                                                                 (pH 2.3 at 27° C.)                                ______________________________________                                    

In comparison with the known processing system for forming asilver-based sound track, the above described processing methodcomprising a bleaching step with the above-described persulphate bleachbath offers an important advantage in that it. does not include a seconddevelopment and requires but one fixing step.

An even further simplification of the above described processing can berealized by using a bleach-fixing (blix) bath. In that case theprocessing sequence can be reduced to a treatment with successively theprebath, the colour developing bath, the stopbath, all three asdescribed above, then treatment with the blix-bath having the followingcomposition, rinsing, and treatment with the above described stabilizingbath.

Composition of the blix bath:

    ______________________________________                                        water                 700      ml                                             sodium sulphite       10       g                                              mercaptotriazole      2.5      g                                              ethylene diamine tetraacetic acid                                                                   13       g                                              tetrasodium salt                                                              ethylene diamine tetraacetic acid                                                                   50       g                                              iron salt                                                                     ammonium bromide      10       g                                              ethylene diamine tetraacetic acid                                                                   5        g                                              ammonium thiosulphate 150      g                                              water to make         1000     ml.                                                                (pH 6.3 at 27° C.)                                 ______________________________________                                    

In order to facilitate evaluation of the quinone imine dye sound tracksformed, samples were prepared of photographic elements as describedhereinbefore with the difference that no image-recording layers werecoated onto the subbed film support. The samples were exposed through astep wedge having a constant of 0.5, the density steps of which rangefrom density 0.5 at step 1 to density 3 at step 6, to light so as toaffect the sound-recording layers. The samples were then processed asdescribed hereinbefore for the multilayer colour photographic motionpicture elements containing image-recording layers also.

In the accompanying FIGS. 1 to 8 a plot of density D versus wavelength(in nm) of the quinone imine dye images obtained is shown. The differentcurves of a plot refer to different consecutive steps of the step wedge,through which the sample was exposed.

Comparison of the plots shows that the absorption peaks in FIGS. 1 and 2(comparison couplers A and B respectively dispersed with dibutylphthalate) range between 740 for the lower curve and 800 nm for theupper curve, whereas the absorption peak in FIG. 3 (coupler 1 dispersedwith dibutyl phthalate) ranges between 750 for the lower curve and 860nm for the upper curve, which is well into the infrared region, and theabsorption peaks in FIGS. 4 to 6 (coupler 1 dispersed with theoil-formers indicated in Table 2) and in FIG. 7 (coupler 2) are near 870nm for both the lower curve and the upper curve, which is even fartherinto the infrared region.

Further comparison of the plots shows that the absorption ranges of thedyes obtained from comparison couplers A and B in FIGS. 1 and 2 arenarrower than those of couplers 1, 2, and 4 in FIGS. 3 to 8, which inthe lower curves appear to have two absorption peaks resulting in onebroadened composite peak that encompasses the whole sensitivity range ofthe S-1 photocells.

Comparison of the infrared spectra of the dyes in FIGS. 1 to 8 clearlydemonstrates that the values of infrared absorption above 850 nmobtained for the dyes derived from 1, 2, and 4 substantially exceedthose of the dyes derived from the comparison couplers. For clarity areference line has been drawn at wavelength 850 nm in each Figure.

EXAMPLE 2

As referred to in the above Example 1 samples were made ofsound-recording layers coated on subbed film supports. The samples wereidentical, except for the composition of the sound-recording layer. Thedifference in the composition of the sound-recording layers onlyreferred to the nature of the coupler and the oil-former used therein.These couplers and oil-formers are identified in the following Table 3.

                  TABLE 3                                                         ______________________________________                                                                       refer to                                       Coupler Oil-former             FIG. No.                                       ______________________________________                                        Compar- dibutyl phthalate       9                                             ison A                                                                        Coupler 1                                                                             1,3-dimethoxy-2-propanol myristic ester                                                              10                                             Coupler 2                                                                             1,3-dimethoxy-2-propanol myristic ester                                                              11                                             Coupler 4                                                                             1,3-dimethoxy-2-propanol myristic ester                                                              12                                             ______________________________________                                    

Comparison A is the known coupler identified in Example 1.

All samples were exposed and processed in the same way as described inExample 1, except that instead of the CD-2 colour developing agent ofExample 1, the CD-3 colour developing agent2-amino-5-[N-ethyl-N-(methylsulphonylamino)-]-aminotoluene sulphate wasused now. It is to be noted that in CD-3 development a higher exposuredose is required to achieve the same density values as in CD-2development.

In the accompanying FIGS. 9 to 12 plots of density D versus wavelength(in nm) of the quinone imine dye sound tracks obtained are shown.

Comparison of these plots learns that the absorption peaks in FIGS. 10to 12 (couplers 1, 2 and 4 dispersed with the oil-former indicated inTable 3) are closer to the infrared region than those obtained with theknown coupler.

Further comparison of the plots also shows that the couplers of thepresent invention give dyes, which show two absorption peaks resultingin one broadened composite peak that covers the sensitivity range of theS-1 photocells in a better way than the peak obtained from the knowndye.

Comparison of the infrared spectra of the dyes in FIGS. 9 to 12 clearlydemonstrates that the values of infrared absorption above 850 nmobtained for the dyes derived from couplers 1, 2, and 4 substantiallyexceed those of the dye derived from the comparison coupler A. Forclarity a reference line has been drawn at wavelength 850 nm in eachFigure.

In consequence of the high density values obtained, the signal to noiseratio of the dye sound tracks made in accordance with the presentinvention exceeds that of the known dye sound track.

Comparable results were obtained with the other couplers of the presentinvention.

We claim:
 1. Photographic element comprising a support and a pluralityof photosensitive silver halide emulsion layers for forming amulticolour photographic dye image and an integral, infrared-absorbing,dye sound track, one of said photosensitive silver halide emulsionlayers or a non-photosensitive hydrophilic colloid layer inwater-permeable relationship therewith comprising at least one dispersed1-hydroxy-2-N-(5-alkylthiazol-2-yl)-naphthamide coupler capable offorming an infrared-absorbing quinone imine dye by reaction with anoxidized aromatic primary amino developing agent, wherein saidnaphthamide coupler bears on the thiazol-2-yl group a 4-para-C₁ -C₄alkoxyphenyl group or a 4-para-C₁ -C₄ -alkylphenyl group, the hydrogenatoms of said C₁ -C₄ alkoxy or C₁ -C₄ alkyl being unsubstituted or atleast one of them having been substituted by a halogen atom.
 2. Aphotographic element according to claim 1, wherein said naphthamidecoupler corresponds to the following general formula: ##STR4## whereinrepresent: R--a C₁ -C₄ alkoxy group, a C₁ -C₄ alkyl group, or a C₁ -C₄alkoxy group or C₁ -C₄ alkyl group wherein at least one of the hydrogenatoms has been replaced by a halogen atom;Y--an alkyl group having atleast 8 carbon atoms; Z--hydrogen or a substituent that splits offduring the coupling reaction, thus conferring 2-equivalent character tothe coupler.
 3. A photographic element according to claim 2, wherein Ris methoxy or ethoxy, Y is tetradecyl, and Z is chloro.
 4. Aphotographic element according to claim 1, comprising:a support, animage-recording layer pack comprising in any desired sequence at leastone image-recording blue-sensitive gelatin silver halide emulsion layercontaining at least one yellow image dye-forming coupler at least oneimage-recording red-sensitized gelatin silver halide emulsion layercontaining at least one cyan image dye-forming coupler, at least oneimage-recording green-sensitized gelatin silver halide emulsion layercontaining at least one magenta image dye-forming coupler, and one ormore intermediate layers between said image-recording emulsion layers, aphotosensitive sound-recording gelatin silver halide emulsion layer, andan antistress layer, said photosensitive sound-recording layer and/or anon-photosensitive hydrophilic colloid layer in water-permeablerelationship therewith comprising said1-hydroxy-2-N-(5-alkyl-thiazol-2-yl)-naphthamide coupler.
 5. Aphotographic element according to claim 1, wherein said naphthamidecoupler has been dispersed in one of said photosensitive silver halideemulsion layers or in said non-photosensitive hydrophilic colloid layerin water-permeable relation- ship therewith with the aid of at least onehigh-boiling substantially water-insoluble oil-former.
 6. A photographicelement according to claim 5, wherein said oil-former is at least one ofthe class of substituted 2-propanols and carboxylic, phosphoric, andphosphonic acid esters thereof.
 7. A photographic element according toclaim 6, wherein said oil-former is at least one selected from the groupconsisting of the 2-ethylhexanoic acid ester of1,3-di-n-octyloxy-2-propanol, the myristic acid ester of1,3-dimethoxy-2-propanol, the 2-ethylhexanoic acid ester of1-n-butoxy-3-(2'-ethyl-n-hexyloxy-2-propanol, the myristic acid ester of1-methoxy-2-propanol, and the 2-ethylhexanoic acid ester of1,3-di-n-hexyloxy-2-propanol.
 8. A photographic element according toclaim 5, wherein said oil-former is used in amounts ranging from 0.5 to2 parts by weight relative to the amount of said1-hydroxy-2-N-(5-alkyl-thiazo-2-yl)-naphthamide coupler dispersedtherewith.